Exploring Synthetic Routes to Heteroleptic U^III, U^IV, and Th^IV Bulky Bis(silyl)amide Complexes

Abstract

The bis(silyl)amide {N(SiMe 3

Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes

“…Low carbon values were consistently obtained in microanalysis experiments of 4 and 7 . As <5% protic impurities were seen in the 1 H-NMR spectra of these samples, we attribute this observation to the formation of silicon carbides; we have commented previously that this can lead to incomplete combustion of complexes of these bis(silyl)amides [17,18,19,20,21,22]. …”

“…The synthesis of lithium salts is facile, with n BuLi effecting deprotonation at room temperature; sodium salt preparation is less straightforward as either refluxing conditions or the use of a non-standard reagent such as n BuNa is required. We envisage that these lighter congeners will find synthetic utility as alternative ligand transfer agents to the potassium bis(silyl)amides that we have used extensively in the preparation of f-block complexes [14,15,16,17,18,19,20,21]. Whilst the potassium salts have proved effective in salt metathesis reactions with metal iodide precursors due to facile potassium iodide elimination, we envisage that the lithium and sodium reagents herein could give improved yields when metal chlorides are used as starting materials.…”

“…We have utilized the potassium salts of these ligands to synthesize a catalogue of low-coordinate s- and f-block complexes by salt metathesis methodologies [15,16,17,18,19,20,21,22]. In these previous studies, we found that the potassium bis(silyl)amides generally react with metal iodide precursors to give target complexes in moderate crystalline yields but for metal chloride precursors poor yields have resulted.…”

Preise der Royal Society of Chemistry 2018

“…Mills synthetisiert f‐Element‐Komplexe mit ungewöhnlichen geometrischen Motiven, die interessante Reaktivitäten und magnetische oder physikalische Eigenschaften zeigen können. Im European Journal of Inorganic Chemistry berichtete er über heteroleptische U III ‐, U IV ‐ und Th IV ‐Bis(silyl)amid‐Komplexe …”

Royal Society of Chemistry Prizes and Awards 2018

“…Mills is interested in the synthesis of f‐element complexes with unusual geometrical features, which can engender interesting physical properties such as reactivity and magnetism. He has reported in the European Journal of Inorganic Chemistry on heteroleptic U III , U IV , and Th IV bis(silyl)amide complexes …”